Method and device for manufacturing a thin film and magnestic recording medium

ABSTRACT

A method and a device for manufacturing a thin film by a vacuum deposition method, and a magnetic recording medium produced thereby are disclosed. A thin film of high quality is mass-produced while introducing reaction gas to a thin film forming section from a nozzle consisting of minute tubes, so that the flow of evaporated atoms is not disturbed by the reaction gas.

This appln is a continuation of Ser. No. 09/004,078 Jan. 7, 1998 whichis a div of Ser. No. 08/513,539 Aug. 10, 1995 U.S. Pat. No. 5,759,710.

FIELD OF THE INVENTION

This invention relates to a method and a device for manufacturing a thinfilm, and further relates to a magnetic: recording medium. Morespecifically, this invention relates to a device and a method ofmanufacturing a thin film and a magnetic recording medium useful formagnetic tapes.

BACKGROUND OF THE INVENTION

In modern society, thin films are widely used in our daily life.Particularly, thin films used for wrapping paper, magnetic tapes,capacitors, etc. are manufactured by a continuous winding vacuumdeposition method which allows for high speed mass production. Researchand development of thin film magnetic recording media is widelypracticed so as to increase recording density. Among highly densemagnetic recording thin film media, Co oxide-based thin films arepopular, being commercialized for video tapes.

As a method of manufacturing tape-type Co oxide-based thin film magneticrecording media, the continuous winding vacuum deposition method(Journal of the Magnetic Society of Japan. Vol. 18, Supplement, No. S1(1994), Proceedings of the Third Perpendicular Magnetic RecordingConference '94, page 439-442) is generally applied. The method isexcellent in its productivity. A conventional continuous winding vacuumdeposition method is explained by FIG. 2. Referring to the figure, anelectron beam 6 is irradiated so as to deposit magnetic layer on a filmon a long macromolecular substrate 4 while the substrate is runningalong the surface of a cylinder can 5. As a result, magnetic recordingmedia are mass produced. In other words, long macromolecular substrate 4is unwound from a unwinding roller 3 in a rotating direction 12 in avacuum container 2, which is vacuum exhausted by an exhaust system 1.The substrate is irradiated by means of electron beam 6 while thesubstrate is running along the surface of cylinder can 5. After thesubstrate is deposited by an electron beam deposition source 7 at theaperture of a shielding plate 9, it is wound by a winding roller 10.Reaction gas is introduced from a gas-introducing nozzle 8 so as tocarry out reactive deposition. In the figure, 10 is the winding roller,11 is a guide roller, 12 indicates the rotating direction, and 21 is anelectron gun. Co or Co—Ni is used as a magnetic material. Since thereactive deposition are carried out in an oxygen atmosphere byintroducing oxygen from gas-introducing nozzle 8, a long Co—O or Co—Ni—Omagnetic tape is manufactured. Due to the reactive deposition in anoxygen atmosphere, crystal particles constituting the thin film separatemagnetically, thus increasing coercive force. In addition, oxidizedsections formed on the surface of the film and between crystal grainboundaries prevent rust, thereby improving the hardness of the film andits mechanical durability.

As mentioned above, the continuous winding deposition method is suitablefor mass-producing thin films and can improve the properties of a thinfilm by the above-mentioned reactive deposition. However, gas introducedto the deposition atmosphere scatters vaporized atoms even though itimproves the properties of the film. The properties depend on theincidence angle of vaporized atoms into the substrate and the scatteringconditions of the atoms, so that the properties decline when the flow ofvaporized atoms is disturbed by introduced gas. Thus, gas should beintroduced so as not to disturb the flow of vaporized atoms. Inaddition, the recording density of magnetic recording media should beimproved since the amount of information for recording is furtherincreasing with the development of the information age. Besides highrecording density, mass productivity as well as the excellent recordingand reproducing properties of the media are required in manufacturingthe media. In order to reduce media noise and provide high C/N,conventional magnetic recording media should have a two-layered magneticlayer, so that the deposition of a magnetic layer has to be carried outtwice. In order to make the orientation of magnetic particles the same,the second magnetic layer has to be formed after forming the firstmagnetic layer and then winding the first layer, so that theproductivity of the media declines. Therefore, an improvement inrecording density of the media is expected by introducing gas withoutdisturbing the flow of vaporized atoms, while the mass productivity andthe recording and reproducing properties of media are maintained.

SUMMARY OF THE INVENTION

It is an object of this invention to solve the above-mentionedconventional problems by providing a method and a device formanufacturing a thin film and a magnetic recording medium, thusimproving the properties of a thin film by introducing gas withoutdisturbing the flow of vaporized atoms and mass-producing magneticrecording thin films of high quality.

In order to accomplish this object, the first method of manufacturing athin film of the invention is to form a thin film on a substrate by avacuum deposition method. The thin film is formed while introducingreaction gas. The aggregate of gas flux is applied to a thin filmforming section by a nozzle having minute tubes. A metal, an alloy metalor the like is used for the thin film. An example of the thin film isone made of a magnetic material such as Co—O, Co—Ni—O, or the like. Asthe reaction gas, any gas except inert gas can be applied. For instance,oxidizing gas such as oxygen gas, ozone gas or the like is used. Inaddition, nitrogen monoxide, nitrogen dioxide, carbon monoxide, carbondioxide, chlorine gas or the like can also be applied. As, in asputtering method, nitrogen gas functions as reaction gas in anactivating atmosphere such as a high-frequency excitation atmosphere, sothat nitrogen gas can also be applied in an activating atmosphere. Apreferable degree of vacuum for vacuum deposition depends on theevaporating source. However, the degree of vacuum applied for aconventional vacuum deposition method is applied to this invention. Morespecifically, 1×10⁻² torr or less degree of pressure can be applied toform a thin film.

It is preferable that the ratio of the inside diameter (D) of the minutetube to its length (L) is 1:10, or the value of L is greater than 10.

It is also preferable that the ratio of the inside diameter (D) of theminute tube to a center distance between the minute tube and aneighboring minute tube (X) is 1:4, or the value of X is smaller than 4.

It is further preferable that a reaction gas flux from the minute tubeis excited by high-frequency excitation and is then targeted to a filmforming section.

The second method of manufacturing a thin film of the invention is toform a magnetic layer directly or via a bottom layer by an electron beamdeposition method on a long macromolecular substrate which runs along asupporting body in vacuum. Metals used for forming the magnetic layerare deposited on the substrate from a main aperture of a shielding platewhich is applied to regulate the direction of the metals. At the sametime, gas including oxygen is directed to the substrate at thedeposition end side of the main aperture, and oxygen gas flux isdirected to the film-forming area by the sub-aperture from asub-aperture of the shielding plate on the deposition starting side ofthe main aperture.

It is preferable that a 6 nm thick or thicker non-magnetic layer isformed by a reaction deposition method with the flux of oxygen gas fromthe sub-aperture to a film forming section.

It is preferable that a gap between the edge of the main aperture on thedeposition starting side and the supporting body is 5 mm or less.

It is also preferable that the minute tubes having the ratio (D/L),between the length (L) and the inside diameter (D). of 0.1 or less areapplied so as to blow the flux of oxygen gas.

A seamless belt can also be used as the supporting body, though acylindrical can is generally applied.

The third method of manufacturing a thin film of the invention is toform a magnetic layer directly or via a bottom layer by an electron beamdeposition method on a long macromolecular substrate running along asupporting body in a vacuum. Metals used for forming the magnetic layerare deposited on the substrate from the aperture of a shielding platewhich is deposited to regulate the direction of the metals. At the sametime, gas including oxygen is directed to the substrate from thedeposition end side of the aperture, and the flux of oxygen gas isoriented to the middle of the aperture from a nozzle positioned outsidethe gas flow forming the magnetic layer.

It is preferable that a non-magnetic layer is formed somewhere in theaperture by the oxygen gas provided from the nozzle.

It is also preferable that the ratio of the thickness of the magneticlayer on a substrate side relative to the thickness on a surface side is3:1-8:1, when the magnetic layer is divided into the substrate side andthe surface side by the extension line from the center of the nozzle.

A seamless belt can also be used as the supporting body, though acylindrical can is generally applied.

The fourth method of manufacturing a thin film of the invention is toform a magnetic layer directly or via a bottom layer by an electron beamdeposition method on a long macromolecular substrate running along asupporting body in a vacuum. Two apertures are formed in a shieldingplate regulating the direction of metal used for forming the magneticlayer, and the metal is deposited on the substrate from the apertures.The thickness of a magnetic layer which is formed at the first apertureis larger than that of a magnetic layer which is formed at the secondaperture. The flux of gas including oxygen is directed to the substratefrom at least the deposition end of the second aperture.

It is preferable that the magnetic layer formed at the first aperture isfrom three to eight times as thick as the magnetic layer formed at thesecond aperture.

It is also preferable that the flux of gas including oxygen is directedto the substrate from the deposition end of the first aperture.

A seamless belt can also be used as the supporting body, though acylindrical can is generally applied.

The first device for manufacturing a thin film of the invention includesa nozzle which blows reaction gas to a thin film forming section. Thenozzle has of minute tubes.

It is preferable that the ratio of the inside diameter (D) of the minutetube to the length (L) of the tube is 1:10, or the value of L is greaterthan 10.

It is also preferable that the ratio of the inside diameter of theminute tube (D) to a center distance (X) between the minute tube and aneighboring minute tube is 1:4, or the value of X is smaller than 4. Therelation between the inside diameter (D) and the center distance (X) isshown in FIG. 26.

It is further preferable that the device includes a section of thenozzle made of minute tubes and a section for exciting the reaction gasby high-frequency excitation, and that the latter, section is connectedto the former section.

The second device for manufacturing a thin film of the invention forms athin film on a long macromolecular substrate running along a supportingbody in a vacuum. The supporting body is a seamless belt. The deviceincludes a shielding plate, which regulates the direction of atomsapplied to form the thin film, and has a main aperture for depositingthe thin film on the substrate, a nozzle for blowing gas to thesubstrate from the deposition end side of the main aperture, asub-aperture in the shielding plate on the deposition starting side ofthe main aperture, and a nozzle for directing the flux of gas to thefilm-forming area by the sub-aperture from near the supporting body.

The third device for manufacturing a thin film of the invention forms athin film on a long macromolecular substrate running along a supportingbody in a vacuum. The supporting body is a seamless belt. The deviceincludes a shielding plate, which is to control the direction of atomsapplied to form the thin film and is formed with an aperture fordepositing the thin film on the substrate, a nozzle for blowing gas fromthe deposition end of the aperture to the substrate, and a nozzle fororienting the flux of gas from the outside of the passing area of vaporflux forming the thin film.

The fourth device for manufacturing a thin film of the invention forms athin film on a long macromolecular substrate running along a supportingbody in a vacuum. The supporting body is a seamless belt. The deviceincludes a shielding plate, which regulates the direction of atomsapplied to form the thin film and is formed with two apertures fordepositing the thin film on the substrate, and a nozzle for blowing theflux of gas from the deposition end side of each aperture to thesubstrate.

The first magnetic recording medium of the invention includes a thinmagnetic layer formed directly or via a bottom layer on a substrate. Themagnetic layer contains at least Co and O as main components. Themagnetic layer, near its surface. contains more oxygen than other areasof the layer except for the section at the boundaries between itself andthe substrate or the bottom layer. In addition, a section of themagnetic layer at 5 nm or below from its surface and above theboundaries between itself and the substrate or the bottom layer hasroughly constant oxygen. The peak oxygen content at the sectioncontaining more oxygen mentioned above is at least 150 atm % as much asthe average oxygen, amount of the section containing the above-notedconstant oxygen level.

The second magnetic recording medium of the invention includes a thinmagnetic layer formed directly or via a bottom layer on a substrate. Theoxygen signal strength of an Auger Depth profile measured from thesurface of the magnetic layer shows peaks at least at the magnetic layersurface and at the mid-magnetic layer. The peak in the mid-magneticlayer is located at a depth of 11-25% down from the magnetic layersurface. The peak of the mid-magnetic layer is 60% or more as strong asthat of the magnetic layer surface. The Auger Depth profile mentionedabove is a method of carrying out the conventional Auger analysis byetching the thin film surface with an ion. As the ion, an Ar ion isused, and the etching rate is preferably around 2 nm/minute (20angstroms/minute).

It is preferable that the width at half the height of the peak in themid-magnetic layer is 20 nm or less.

It is also preferable that the magnetic layer includes Co and O as maincomponents.

The third magnetic recording medium of the invention includes a thinmagnetic layer via a non-magnetic layer formed on a substrate. Thenon-magnetic layer consists of the oxide of atoms constituting themagnetic layer. The oxygen signal strength of an Auger Depth profilemeasured from the magnetic layer surface has peaks at least on themagnetic layer surface and in the non-magnetic layer. The peak strengthin the non-magnetic layer is at least 70% as much as that of themagnetic layer surface. The thickness on the side of the magnetic layersurface, where the oxygen signal strength of the non-magnetic layer is90-50% as much as its peak, is 20 nm or less.

It is preferable that the magnetic layer contains at least Co and O asmain components.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram showing an embodiment of a method and device formanufacturing a thin film of the invention.

FIG. 2 is a diagram showing an embodiment of a conventional method anddevice for manufacturing a thin film.

FIG. 3 is a diagram showing an embodiment of a gas-introducing nozzle ofthe invention.

FIG. 4 is a graph showing the correlation between the amount ofintroduced oxygen and film properties of the invention when the insidediameter of a tube (øp) is varied.

FIG. 5 is a graph showing the results of an Auger Depth profile of theinvention while the inside diameter of a tube (øp) is changed.

FIG. 6 is a graph showing the correlation between the amount ofintroduced oxygen and film properties of the invention when the lengthof a nozzle edge is changed.

FIG. 7 is a diagram showing an embodiment of a two-stage nozzle of theinvention.

FIG. 8 is a graph showing the correlation between the amount ofintroduced oxygen and film properties of the invention whenhigh-frequency electric power is changed.

FIG. 9 is a diagram showing an embodiment of a method and device formanufacturing a thin film of the invention.

FIG. 10 is a graph showing the correlation between the thickness of anon-magnetic layer and the recording and reproducing properties of athin film of the invention.

FIG. 11 is a graph showing the recording and reproducing properties of athin film, when a macromolecular substrate is wound after being providedwith a non-magnetic layer and is then provided with a magnetic layer.

FIG. 12 is a graph showing the recording and reproducing properties of athin film of the invention when the mouth shape of a gas introducingsub-nozzle is changed.

FIG. 13 is a graph showing an example of an Auger Depth profile of amagnetic recording medium of the invention.

FIG. 14 shows an embodiment of a method and device for manufacturing athin film of the invention.

FIG. 15 is a graph showing the recording and reproducing properties of amagnetic tape of the invention which is manufactured by changing theamount of oxygen introduced from a sub-nozzle.

FIG. 16 is a graph showing the correlation between the recording andreproducing properties of a thin film and the shape of a sub-nozzle ofthe invention.

FIG. 17 is a diagram showing the shape of a sub-nozzle of the invention.

FIG. 18 is a graph showing an example of an Auger Depth profile of amagnetic recording medium of the invention.

FIG. 19 is a diagram showing an embodiment of a method and device formanufacturing a thin film of the invention.

FIG. 20 is a graph showing the recording and reproducing properties of athin film of the invention when oxygen gas is introduced only from thedeposition end of a first aperture.

FIG. 21 is a graph showing the recording and reproducing properties of athin film of the invention when oxygen gas is introduced from thedeposition end of both first and second apertures.

FIG. 22 is a graph showing an example of an Auger Depth profile of amagnetic recording medium of the invention.

FIG. 23 is a diagram showing an embodiment of a method and device formanufacturing a thin film of the invention when a belt is used as asupporting body for a macromolecular substrate.

FIG. 24 is a diagram showing an embodiment of a method and, device formanufacturing a thin film of the invention when a belt is used as asupporting body for a macromolecular substrate.

FIG. 25 is a diagram showing an embodiment of a method and device formanufacturing a thin film of the invention when a belt is applied as asupporting body for a macromolecular substrate.

FIG. 26 is a diagram showing the corretion between the inside diameterof a minute tube of the gas introducing nozzle and, the center distanceof neighboring tubes.

DETAILED DESCRIPTION OF THE INVENTION

This invention will be described by referring to the followingillustrative examples and attached figures.

Example 1

The first example is explained by referring to FIG. 1. A, longmacromolecular substrate 4 is unwound from an unwinding roller 3 in arotational direction 12 in a vacuum container 2, which is, vacuumexhausted by an exhaust system 1. A deposit is formed or the substrateat the aperture of a shielding plate 9 by an evaporating source 7 whichis irradiated with an electron beam 6, while the substrate is runningalong the surface of a cylindrical can 5. Then, the substrate is woundby a winding roller 10. Reaction and deposition can be carried out byintroducing reaction gas from a gas-introducing nozzle 8. In order toincrease the adherence between the macromolecular substrate and the can,the substrate can be pressed against the can by a nip roller 16 andirradiated with an electron beam 14 used for providing adherence from anelectron gun 13. The nip roller and the electron gun can be removed fromthe device when they are unnecessary.

As an example of manufacturing a thin film magnetic tape, a 2000 m long,200 mm wide and 10 μm thick polyethylene terephthalate film was used asa macromolecular resin substrate (film or sheet). With 40 m/minutewinding speed and oxygen gas as the reaction gas, two 70 nm thick Co—Omagnetic layers were laminated. The incidence angle of vapor to thefirst and the second layer was from 70 to 50 degrees relative to thenormal line of the substrate. The extension line of the gas-introducingnozzle was directed toward a deposition end section. The cylindrical canwas cooled by cooling water circulating inside the can and having anordinary temperature. The degree of vacuum in the deposition chamberduring the film forming process was about 5×10⁻⁵ torr.

The properties of the magnetic tape were evaluated by the coercive forcemeasured by a vibrating sample magnetometer, aid recording andreproducing properties measured by a MIG head. The recording andreproducing properties of the magnetic tape were measured by comparingits C/N at 0.5 μm recording wavelength with the C/N of a deposition tapeused for videos sold on the market (ME tape). Scratch tests based on theJIS-K 6718 testing method were also carried out on some samples.

The magnetic tape was manufactured by using a gas-introducing nozzleshown in FIG. 3, and the properties of the tape were compared with thoseof another tape manufactured by using a nozzle with different shapes.The nozzle shown in FIG. 3 has multiple tubes at the end, and isconnected to a gas-introducing pipe so as to provide almost the sameamount of gas to each tube.

The inside diameter (øp) of the tube was changed, and the number oftubes was arranged so as to keep the total internal tube area constant.The magnetic layer was formed by directing oxygen gas to a layer formingsection. The length of the subdivided nozzle section was fixed to 30 mm.The distance between the nozzle edge and the substrate was 100 m.

FIG. 4 shows the correlation between the amount of introduced oxygen andfilm properties when the inside diameter (øp) of the tube was changed.According to the figure, high coercive force is obtained with a smallamount of oxygen as the inside diameter (øp) becomes small. At the samelevel of coercive force, high C/N is obtained as the inside diameter(øp) becomes small. In other words, film properties are improved whensubdivided gas is introduced. This is because the collision among gasatoms inside the tube is reduced, and the flow of gas is uniformlyoriented along the lengthwise direction of the nozzle. Thus, byefficiently orienting the reaction gas to a reaction region of the thinfilm, the flow of vaporized atoms becomes less disorderly. Furthermore,at the same coercive force, not only high C/N but also improvedendurance is obtained by subdividing the flow of the reaction gas. Forexample, a medium having 1400 oersted coercive force was used for ascratch test, and the medium with øp=1.5 mm or 0.2 mm had a scratchstrength which is 1.5 or 2 times as strong as the scratch strength of amedium with øp=3 mm. This is probably because of an increase in thepacking factor of the thin film from reducing the amount of introducedgas. It is extremely important to provide a magnetic recording mediumhaving not only excellent recording and reproducing properties but alsoother properties; particularly in a thin film magnetic recording medium,an advanced technique to maintain mechanical properties with a thin filmthickness is required. In this sense, this invention is useful. In orderto test the difference in film structures by subdividing introduced gas,a medium with 1400 oersted coercive force was applied so as to measurean Auger Depth profile at øp=0.2 mm and 3 mm. The results are shown inFIG. 5. As shown in the figure, an oxidized area near the surface of themagnetic layer is formed more distinctively at øp=0.2 mm than the areaat øp=3 mm. The magnetic layer formed with øp=0.2 mm has almost constantoxygen density except at an initially grown section and a thin oxidizedarea close to the surface. As mentioned above, the collision among gasatoms inside the nozzle is reduced, and the direction of reaction gasflow is oriented to the lengthwise direction of the nozzle edge which isshown in FIG. 3. Thus, the reaction gas was efficiently directed to areaction region. According to the results shown in FIG. 5, theproperties of a magnetic recording medium are excellent when theoxidized area close to the magnetic layer surface is formeddistinctively and the oxygen density is almost constant, except for athin oxidized area close to the magnetic layer surface and an initiallygrown section. In the figure, a section with abundant oxygen is withinthe region of 8 nm from the magnetic layer surface, when øp is 3 mm. Thesection is within the region of 5 nm and 3 nm from the surface when øpis 1.5 mm and 0.2 mm, respectively. Therefore, it is preferable that thearea with abundant oxygen lies 5 nm or less from the magnetic layersurface.

The edge length of the gas-introducing nozzle having minute tubes with0.6 mm inside diameter was changed. FIG. 6 shows the correlation betweenthe amount of introduced oxygen and film properties when the length ofthe nozzle edge (K) relative to the inside diameter is changed.According to the figure, when the nozzle edge length is ten times ormore as long as the inside diameter, high coercive force and C/N areobtained. As the ratio between the nozzle edge length and the insidediameter becomes large, the properties of a thin film improve. This isbecause the flow of reaction gas from the nozzle becomes orderly.Therefore, in order to utilize the gas-introducing nozzle includingminute tubes at the edge, the ratio (K) of a nozzle edge length relativeto an inside diameter of the tube should be set at a certain high level.More specifically, the ratio should be ten or more.

In addition, the thickness of a minute tube was changed while the insidediameter of the tube was set constant, so that film properties weretested while the ratio of the inside diameter of a minute tube relativeto a center distance between the minute tube and a neighboring minutetube was varied. As a result, high coercive force and C/N are achievedwhen the center distance is four times or less as large as the insidediameter. This is because the flow of introduced gas molecules worksuniformly as reaction gas. When the center distance is too largerelative to the inside diameter, the effect of such a gas-introducingnozzle is insignificant; therefore, the ratio should be four or less.

Example 2

A two-stage gas-introducing nozzle shown in FIG. 7 is applied in thisexample. The first stage 19 of the nozzle shown in the figure isbasically the same as the one shown in FIG. 3. However, at the secondstage 20 of the nozzle, high-frequency electric power is applied toexcite introduced gas. 13.56 MHz high-frequency electric power wasapplied to the first stage having a 30 mm long subdivided section whichconsists of minute tubes with 0.2 mm inside diameter. FIG. 8 shows thecorrelation between the amount of introduced oxygen and film propertieswhen high-frequency electric power is varied. As shown in the figure,high coercive force is obtained with less oxygen by addinghigh-frequency electric power to the oxygen. At the same coercive force,higher C/N is obtained with the application of high-frequency electricpower. In other words, the properties of a thin film improve whenhigh-frequency electric power is added to the introduced gas. This isbecause a part of the reaction gas is excited, and is ionized or becomesradical, thus increasing its reactivity. With the improved reactivity ofintroduced gas, the amount of gas required for obtaining high coerciveforce can be reduced, and reactive deposition can be carried out withoutdisturbing a vaporized atom flow, so that the properties of a thin filmimprove.

As described in Examples 1 and 2, reactive deposition can be carried outefficiently with a small gas flow by applying a gas-introducing nozzlewhose edge has numerous minute tubes and by orienting a reaction gasflow with a strong directivity to a film forming section. As a result,the properties of a thin film improve, increasing coercive force andC/N. In addition, when some reaction gas is excited, reaction efficiencyfurther improves, thus improving the properties of a thin film.

In Examples 1 and 2, the recording and reproducing properties of a thinfilm were evaluated by coating lubricant on the surface of a magneticlayer. However, in order to further improve the mechanical properties, aprotective layer can be formed on the surface of a magnetic layer, orlubricant can be coated on the protective layer in the invention.

Example 3

The third example of this invention is explained by referring to FIG. 9.A long macromolecular substrate 4 is unwound from an unwinding roller 3in a rotational direction 12 in a vacuum container 2 which is vacuumexhausted by an exhaust system 1. A deposit is formed on the substrateat the aperture of a shielding plate 9 by an evaporation source 7 whichis irradiated with an electron beam 6, while it is running along thesurface of a cylindrical can 5. Then, the substrate is wound by awinding roller 10. In order to increase the adherence between themacromolecular substrate and the can, the substrate can be pressedagainst the can by a nip roller 16 and then irradiated with an electronbeam 14 used for adding adhesion from an electron gun 13. The surfacetreatment or the like of the substrate can also be carried out by usingan ion source. The nip roller and the electron gun can be removed fromthe device when they are unnecessary.

Reaction and deposition were carried out by directing gas includingoxygen to the substrate from a main nozzle 21 on the deposition end ofthe aperture. The flux of oxygen gas was applied to the film-formingarea by the sub-aperture from a sub-nozzle 22 from the top of theshielding plate aperture edge on the deposition starting side. Inaddition, a sub-aperture was formed in the shielding plate on thedeposition starting side. Some of the vapor flow passing through thesub-aperture adhered to the substrate, and the flux of oxygen gas wasdirected mainly to the section of the substrate where the vapor passingthrough the sub-aperture adhered. The internal size of the sub-nozzlewas 200×6×30 mm and had a box shape. The mouth was 200 mm wide in thedirection of a substrate width and 6 mm long. The gap between theshielding plate edge on the deposition starting side and the supportingbody was changed within the range of 1 m and 10 mm, and the propertiesof a thin film magnetic tape were compared.

The extension line of gas-introducing main nozzle 21 was oriented to theaperture on the deposition end side. The extension line of sub-nozzle 22was targeted mainly to the area where vapor passing through thesub-aperture adhered to the substrate. A cylindrical can was cooled bycooling water circulating inside the can and having an ordinarytemperature. The degree of vacuum in the deposition chamber was about5×10⁻⁵ torr.

As the macromolecular substrate, a 30 cm wide and 10 μm thickpolyethylene terephthalate film was used, and a 200 nm thick Co—Omagnetic layer was formed. The incidence angle of vapor to themacromolecular substrate was from 80 to 40 degrees from the normal lineof the substrate. The sub-aperture was formed in the shielding plate onthe deposition starting side. Besides the 200 nm thick magnetic layer,0-40 nm thick non-magnetic or low-saturation magnetization Co—O wasformed before the deposition of the magnetic layer. In case of zerothickness Co—O by sub-aperture, sub-aperture was closed.

The thickness of the magnetic layer was measured by a film thicknessmeasuring device using transmitted light which was deposited betweenguide rollers while the layer was deposited. The thickness wascontrolled by arranging the electric power of an electron gun. Themeasuring device consisted of a visible light source and a CDS element.

The magnetic properties of the magnetic layer were measured by avibrating sample magnetometer. The recording and reproducing propertiesof the layer were evaluated with a MIG head. The C/N at 0.5 μm recordingwavelength of this magnetic layer was compared with the C/N of adeposition tape which is used for videos sold on the market (ME tape).

As shown in FIG. 10, the recording and reproducing properties of thelayer improve significantly by forming a magnetic: layer after forming anon-magnetic layer. Especially when the non-magnetic layer is 6 nm thickor more, the properties improve significantly, so that the thickness ofthe layer is preferably 6 nm or more. The properties also improvesignificantly when the gap between the shielding plate edge on thedeposition starting side and the cylindrical can is 5 mm or less.However, if the gap is more than 5 mm, the properties decline as the gapwidens. This is probably because oxygen gas from the sub-nozzle swirlsabout the aperture, thus disturbing the initial growth of the magneticlayer. Therefore, the gap between the shielding plate edge and thecylindrical can is preferably 5 mm or less.

Comparative Example 1

The same method as the method in Example 3 was applied in this example,except that a magnetic layer was formed after forming a non-magneticlayer and winding a macromolecular substrate, and that no sub-aperturewas formed. The recording and reproducing properties were measured, andthe results are shown in FIG. 11.

As found by comparing FIG. 10 to FIG. 11, the recording and reproducingproperties of a thin film manufactured by forming a magnetic layer rightafter forming a non-magnetic layer as in Example 3 are superior to thoseof a thin film which is manufactured by first forming a non-magneticlayer and then winding the substrate and then forming a magnetic layer.This is because the surface of the non-magnetic layer remains clean whenthe substrate is not wound before being formed with the magnetic layer.Thus, if the magnetic layer is formed right after forming thenon-magnetic layer, the properties of the magnetic layer also improve.

Example 4

FIG. 12 shows the recording and reproducing properties of a thin filmwhen the same method as in Example 3 was applied to form the film andthe shape of edge of gas-introducing sub-nozzle 22 was changed. Theinternal size of the sub-nozzle was 200×6× Lmm, and the mouth was widein the direction of a substrate width and was 200×6 mm. L was changed to5, 10 and 20. Stainless minute tubes were filled in the sub-nozzle, sothat the introduced gas was the aggregated flux of gas from the minutetubes. Though the inside diameter (D) of the tube varies from 0.5 mm to2 mm, 1 m is mostly selected. As shown in FIG. 12, the recording andreproducing properties of a film improved, when L/D is 10 or more andthe aggregated flux of gas was applied. In other words, when asub-aperture was formed in the shielding plate on the depositionstarting side and a non-magnetic layer was formed before the depositionof a magnetic layer, the properties improved by setting L/D equal to 10or more with the application of the minute tubes. This is because theswirl of oxygen gas about a magnetic layer forming section is minimized.

FIG. 13 shows the signal strength of Co and O of an Auger Depth profilearound the magnetic layer section of the magnetic recording media formedin Examples 3 and 4. In the Auger Depth profile of FIG. 13, C/N shown inFIG. 10 is found when the oxygen peak C at the non-magnetic orlow-saturation magnetization bottom layer is 70% or more of the oxygenpeak A at the magnetic layer surface. From the magnetic layer side, thecorrelation between the thickness of the non-magnetic layer with 90-50%oxygen signal strength relative to its peak and the gap of the shieldingplate edge on the deposition starting side and the cylindrical can weretested. It was found that 20 nm or less thickness with 90-50% oxygensignal strength of the non-magnetic layer relative to its maximum couldbe obtained when the gap was 5 m or less. As in Example 4, when thesub-nozzle made of the aggregated minute tubes was applied, thethickness of the non-magnetic layer with 90-50% oxygen signal strengthrelative to its peak was further lessened The properties of a thin filmimprove by applying such a sub-nozzle probably because the lower rangeof oxygen signal strength of the non-magnetic layer is narrowed and theboundary between the non-magnetic layer and the magnetic layer becomesclearly distinctive.

In Examples 3-4, a Co—O non-magnetic layer was formed at the initialgrowth period of a thin film by using a Co evaporating source. As amagnetic material, another metal or alloy can also be applied. Forexample, when a Co—Ni alloy evaporating source is applied, the samemethod can be applied so as to form a Co—Ni—O magnetic layer afterforming a Co—Ni—O non-magnetic layer. It is also possible to introduceoxygen in depositing two sources including Co and Ni.

Example 5

The fifth example of this invention is explained. As shown in FIG. 14, along macromolecular substrate 4 is unwound from an unwinding roller 3 ina rotating direction 12 in a vacuum container 2 which is vacuumexhausted by an exhaust system 1. A deposit is formed on the substrateat the aperture of a shielding plate 9 by the vapor from an evaporationcrucible 7 which is irradiated with an electron beam 6, while thesubstrate is running along the surface of a cylindrical can 5. Then, thesubstrate is wound by a winding roller 10. In order to increase theadherence between the macromolecular substrate and the can, thesubstrate can be pressed against the can by a nip roller 16 and thenirradiated with an electron beam 14 used for providing adherence from anelectron gun 13. The nip roller and the electron gun can be removed fromthe device when they are unnecessary.

Gas including oxygen is directed to the substrate on the deposition endside of the aperture, and the flux of oxygen gas is oriented to themiddle of the aperture from a sub-nozzle which has minute tubes and ispositioned outside the vapor flow.

In order to manufacture a thin film magnetic tape, 30 cm wide and 10 gmthick polyethylene terephthalate was applied as a macromolecularsubstrate. A 200 nm thick Co—O magnetic layer was formed. The incidenceangle of vapor to the macromolecular substrate is from 80 to 40 degreesrelative to the normal line of the substrate. The extension line of amain nozzle 21 was oriented to the deposition end section, and theextension line of sub-nozzle 22 crossed the substrate on the cylindricalcan at the point of the vapor incidence angle of 48 degrees. Thecylindrical can was cooled by cooling water which was circulating in thecan and had an ordinary temperature. The degree of vacuum in thedeposition chamber was about 5×10⁻⁵ torr.

The magnetic layer of this example was evaluated by the same method asin Example 3.

FIG. 15 shows the recording and reproducing properties of a magnetictape which was manufactured by changing the amount of oxygen introducedfrom the sub-nozzle. As shown in FIG. 15, C/N improves as oxygen isintroduced from the sub-nozzle. This is because a non-magnetic layer ora low-saturation magnetization layer was formed in the mid-growth of themagnetic layer by introducing oxygen from the sub-nozzle, so that noisewas reduced and C/N improved since the magnetic layer including thenon-magnetic or low-saturation magnetization layer had a pseudotwo-layer structure. The formation of the non-magnetic layer or thelow-saturation magnetization layer in the mid-growth of the magneticlayer was estimated from the Auger Depth profile of the medium. When theamount of oxygen introduced from the sub-nozzle was too great, vapor wasscattered by the gas, so that the recording and reproducing propertiesdeclined. The properties improve significantly when the magnetic layeris divided by the extension line of the sub-nozzle and the thicknessratio of a section of the magnetic layer on the substrate side relativeto another section on the surface side ranges from 3:1 to 8:1.

FIG. 16 shows the correlation between the shape of the sub-nozzle andthe recording and reproducing properties of a thin film. As in FIG. 17,the shape of the sub-nozzle was changed by varying the ratio of nozzlelength in a blowing direction (L) relative to nozzle mouth height (A),and the relationship between A/L and the recording and reproducingproperties was tested. In FIG. 17, a cylindrical pipe was formed withnumerous minute oval holes in the lengthwise direction. The amount ofoxygen from the sub-nozzle was 10SCCM. A/L was 0.2 in FIG. 15. As aresult, as shown in FIG. 16, excellent recording and reproducingproperties are obtained with 0.2 or less A/L. As A/L becomes small,oxygen flowing from the sub-nozzle reaches the macromolecular substrateas aggregated flux, so that an intermediate non-magnetic layer is formeddistinctively. Therefore, the shape of the sub-nozzle should be chosenso as to provide 0.2 or less A/L. In addition, the recording andreproducing properties were improved in Example 5 by applying thesub-nozzle having numerous minute tubes as described in Example 4 andsetting L/D equal to 5 or more.

The signal strength of Co and oxygen around the magnetic layer of themagnetic recording medium manufactured in Example 5 was measured by anAuger Depth profile, and is shown in FIG. 18. A section where oxygenpeak B in the mid-magnetic layer is at least 70% as strong as oxygenpeak A at the magnetic layer surface in FIG. 18 corresponds to a sectionon the right side from where C/N is increasing in FIG. 15. The increasein C/N was clear when T2/(T1+T2) was equal to 11-25%. T1 and T2 are thefirst and the second part of half the width of Co signal, which isdivided by the oxygen peak in the middle of the magnetic layer. T1 isthe thickness of the first layer on the substrate side, and T2 is thethickness of the second layer on the magnetic layer surface side. Theratio of the first relative to the second layer of the pseudotwo-layered magnetic layer is changed by varying the direction of theextension line of the sub-nozzle.

With respect to A/L shown in FIG. 17 and the width at half the height ofthe oxygen peak found in the mid-magnetic layer, the width is 20 nm orless when A/L is 0.2 or less. The improvement in properties is clearwhen A/L is 0.2 or less. By applying the sub-nozzle consisting of minutetubes, the width is 20 nm or less when L/D is 5 or more. In any case,the width at half the height of the oxygen peak found in themid-magnetic layer becomes large when the amount of oxygen introducedfrom the sub-nozzle is too great.

Example 6

Another example of this invention is explained. A long substrate 4 isunwound from an unwinding roller 3 in a rotational direction 12 in avacuum container 2 which is vacuum exhausted by an exhaust system 1shown in FIG. 19, and a deposit is formed on the substrate at theaperture of a shielding plate 9 by vapor from an evaporation crucible 7,which is irradiated with an electron beam 6 while it is running alongthe surface of a cylindrical can 5. Then, the substrate is wound by awinding roller 10. The aperture is divided into two parts. By changingthe ratio of the 0width of the first aperture relative to that of thesecond aperture, the contribution rate of film thickness of one aperturerelative to another aperture varied from 10:1 to 1:1. Reaction anddeposition are carried out by introducing the flux of oxygen gas with agas-introducing nozzle 8 from the deposition end side of each aperture.In order to increase the adherence between the macromolecular substrateand the can, the macromolecular substrate is pressed against the can bya nip roller 16, and an electron beam 14 for providing adherence canthen be irradiated from an electron gun 13 before forming a thin film.In addition, an ion source can be applied to carry out the surfacetreatment or the like on the substrate. The nip roller, the electron gunand the ion source can be removed from the device when they areunnecessary.

In order to form a thin film magnetic tape in this invention, 30 cm wideand 10 μm thick polyethylene terephthalate was applied as themacromolecular substrate, and a 200 nm thick Co—O magnetic layer wasformed. The initial incidence angle of vapor to the macromolecularsubstrate was 80 degree from the normal line of the substrate at thefirst aperture, and the closing incidence angle varied from 45 to 54degrees. On the other hand, the initial incidence angle of vapor to themacromolecular substrate varied from 43 to 52 degrees from the normalline at the second aperture, and the closing incidence angle was 40degree. In any case, the space between the first and second apertures,an angle of 2 degrees of incidence angle, was shielded. The extension ofthe gas-introducing nozzle was oriented to the deposition end of eachaperture. The cylindrical can was cooled by cooling water circulating inthe can and having an ordinary temperature. The degree of vacuum in adeposition room during the film forming process was about 5×10 torr.

The nozzles applied in this example include a box-shaped nozzle shown inFIG. 17 with 200×6×30 mm internal size and having a 200×6 mm mouth whichis wider in the direction of substrate width; a box-shaped nozzle with200×3×30 mm internal size and having a 200×3 mm mouth which is wider inthe direction of substrate width; a box-shaped nozzle explained inExample 4 with 200×6×10 mm internal size, being filled with minute tubeshaving 1 mm internal diameter, and having a 200×6 mm mouth which iswider in the direction of substrate width; or a box-shaped nozzle with200×6×10 mm internal size, being filled with minute tubes having 2 mminternal diameter, and having 200×6 mm mouth which is wider in thedirection of substrate width.

The same method as in Example 3 was applied to evaluate the magneticlayer.

FIG. 20 shows the recording and reproducing properties measured byintroducing the flux of oxygen gas only from the deposition end of thesecond aperture and by varying the contribution rate of film thicknessof the first aperture relative to second aperture from 10:1 to 1:1. FIG.20 shows the results obtained from the application of a device with nodivided aperture and a device with a nozzle having no flow aggregatingsection (length L) shown in FIG. 17. As shown in FIG. 20, the propertiesimprove by dividing the aperture. In addition, by applying the nozzlehaving minute tubes, the properties further improve. When the nozzlewith no minute tubes was applied, there was no improvement in theproperties with 0.2 and 0.1 A/L indicated in FIG. 17. When the nozzlefilled with minute tubes was used, the properties improved by changingL/D from 5 to 10. There is no control over the flux of gas in thedirection of substrate width when the nozzle with no minute tubes isapplied, so that the flux is disturbed slightly in such a direction. Onthe contrary, when the nozzle filled with minute tubes is applied, theflow of gas is controlled in the direction of substrate width and theeffect is clearly shown. In addition, as shown in FIG. 20, the recordingand reproducing properties were excellent when the contribution rate offilm thickness of the first aperture relative to the second aperture wasfrom 8:1 to 3:1. If the contribution rate is less than ⅛, the effect ofdividing the aperture becomes so slight that the result would be similarto the one found from the device with no divided aperture. On thecontrary, the rate of covering the entire film with a film having asmall incidence angle relative to zero degree normal line of thesubstrate becomes too large when the contribution rate is more than ⅓.In other words, since a film with insufficient magnetic separation amongcrystals due to a relatively small incidence angle is grown on theoxidized layer formed at the first aperture, noise is likely to generatefrom a film formed at the second aperture, so that the improvement inthe recording and reproducing properties due to the division of apertureis small.

FIG. 21 shows the recording and reproducing properties by introducingthe flux of oxygen gas from the deposition end of the first and secondaperture and by varying the contribution rate of film thickness of thefirst aperture relative to the second aperture from 10:1 to 1:1. Abox-shaped nozzle having 200×6×3 mm internal size and a 200×6 mm mouthwhich is wider in the direction of substrate width was applied. As shownin FIG. 21, the recording and reproducing properties of a thin filmimprove by applying subdivided apertures and by dividing oxygen flow andintroducing the oxygen at a preferable flow amount from the depositionend. Especially when the contribution rate of film thickness of thefirst aperture relative to the second aperture was from 8:1 to 3:1,excellent properties were obtained.

Thus, by dividing an aperture and applying a nozzle made of minutetubes, the recording and reproducing properties of a thin film improve.In order to provide excellent recording and reproducing properties, itis also preferable that the contribution rate of film thickness of thefirst aperture relative to that of the second aperture is from 8:1 to3:1 and that oxygen is introduced separately to the first and secondaperture.

The signal strength of Co and oxygen around the magnetic layer of themagnetic recording medium formed in Example 6 was measured by an AugerDepth profile, and is shown in FIG. 22. A section of Auger Depth profileshown in FIG. 22 where oxygen peak B in the mid-magnetic layer is atleast 60% as strong as oxygen peak A of the magnetic layer surfacecorresponds to a section where C/N is increasing in FIGS. 20 and 21. Theincrease in C/N was clear when T2/(T1+T2) was equal to 11-25%. T1 and T2are the first and second part of half the width of Co signal, which isdivided by the oxygen peak in the middle of the magnetic layer. T1 isthe thickness of the first layer on the substrate, and T2 is thethickness of the second layer on the magnetic surface side. The layerthickness ratio of the two-layered magnetic layer is changed by varyingaperture ratios.

In Examples 1-6, the cylindrical can was applied as a supporting bodyfor the macromolecular substrate. However, a belt-type supporting bodycan also be applied in this invention. A device shown in FIG. 25 canprovide the same effect as in Example 6. In other words, a longsubstrate 4 is unwound from an unwinding roller 3 in a rotationaldirection 12 in a vacuum container 2, which is vacuum exhausted by anexhaust system 1. A deposit is formed on the substrate at the apertureof a shielding plate 9 by an evaporating source 7 which is irradiatedwith an electron beam 6, while the substrate is running along thesurface of a supporting belt 23. Then, the substrate is wound by awinding roller 10. The aperture is divided into two sections. The fluxof oxygen gas is introduced by using a gas-introducing main nozzle 21and a gas-introducing sub-nozzle 22 from the deposition end side of eachaperture so as to react and deposit. The ratio of a first aperture widthin a running direction relative to a second aperture width is determinedby setting the contribution ratio of film thickness of the firstaperture relative to the second aperture from 8:1 to 3:1 so thatexcellent recording and reproducing properties are provided. In order toincrease adherence between the macromolecular substrate and the can, thesubstrate can be pressed against the can by a nip roller, and then anelectron beam used for adherence can be irradiated from an electron gunbefore forming a thin film. As a supporting belt, a metal belt such as aseamless stainless belt and a flexible material such as a macromolecularbelt can be applied. The thickness of the supporting belt is determinedin consideration of heat conductivity or bending properties of amaterial. For instance, when a stainless steel belt is applied, thethickness is preferably from 0.3 mm to 0.6 mm.

The device shown in FIG. 23 can provide the same effect as in Examples 3and 4. In other words, a long substrate 4 is unwound in a rotationaldirection 12 from an unwounding roller 3 in a vacuum container 2, whichis vacuum exhausted by an exhause system 1. A deposit is formed on thesubstrate at the aperture of a shielding plate 9 by an evaporatingsource 7, which is irradiated with an electron beam 6 while thesubstrate is running along the surface of a supporting belt 17. Then,the belt is wound by a winding roller 10.

Reaction and deposition are carried out by providing gas includingoxygen from a gas-introducing main nozzle 21 on the deposition end sideof a main aperture to the substrate. In addition, the flux of oxygen gasis oriented from a sub-nozzle 22 which is on the top side of theshielding main aperture end on the deposition starting side and is closeto the supporting belt. A sub-aperture is applied in the shielding plateon the deposition starting side so as to adhere some of the vaporpassing through the sub-aperture to the substrate. The flow of oxygengas from the sub-nozzle is oriented to a section where vapor passingthrough the sub-aperture adheres to the substrate. Aggregated minutetubes are applied as the sub-nozzle so as to introduce oxygen gas, thusfurther improving the recording and reproducing properties of a thinfilm as described in Example 4. In order to increase adherence betweenthe macromolecular substrate and the can, the substrate can be pressedagainst the can by a nip roller, and an electron beam used for adherencecan then be irradiated from an electron gun before forming a thin film.Furthermore, an ion source can be applied to carry out the surfacetreatment or the like on the substrate. As a supporting belt, a metalbelt such as a seamless stainless belt and a flexible belt such as amacromolecule belt can be used. The thickness of the supporting beltdepends on the heat conductivity and bending properties of a material.For example, when a stainless steel belt is used, the thickness ispreferably about 0.3-0.6 mm.

The device shown in FIG. 24 can provide the same effect as in Example 5.In other words, a long substrate 4 is unwound from unwinding roller 3from a rotational direction 12 in a vacuum container 2, which is vacuumexhausted by an exhaust system 1. A deposit is formed on the substrateat the aperture of a shielding plate 9 by an evaporating source 7irradiated with an electron beam 6, while the substrate is running alongthe surface of a supporting belt 7. The substrate is then wound by awinding roller 10. Oxygen gas is directed to the substrate from thedeposition end of a main aperture. The flux of oxygen gas is oriented tothe middle of the aperture from the sub-nozzle positioned outside ofvapor flux, which is forming the magnetic layer. In FIG. 24, anon-magnetic layer or a low-saturation magnetization layer is formed inthe mid-growth of the magnetic layer by introducing oxygen from thesub-nozzle. As a result, the magnetic layer has a pseudo two-layerstructure, thus lowering noise and improving C/N. The formation of anon-magnetic layer or a low-saturation magnetization layer in themid-growth of the magnetic layer was estimated from the Auger Depthprofile of the medium. In order to increase adherence between themacromolecular substrate and the can, the substrate can be pressedagainst the can by a nip roller, and an electron beam for generatingadherence can then be irradiated from an electron gun before forming athin film. Furthermore, an ion source can also be applied to carry outthe surface treatment or the like on the substrate. As a supportingbelt, a metal belt such as a seamless stainless belt and a flexible beltsuch as a macromolecule belt can be applied. The thickness of asupporting belt depends on the heat conductivity and bending propertiesof a material. For example, when a stainless steel belt is applied, thethickness is about from 0.3-0.6 mm.

Polyethylene terephthalate was applied as a substrate in Examples 1-6.However, other materials including macromolecular materials such aspolyethylene naphthalate, polyolefine, polyamide and polyimide can alsobe applied as a substrate. In addition, even though only the formationof a Co—O magnetic layer was described in the examples, the same effectis expected by applying another oxide thin film such as Co—Ni—O. Theinvention is also effective when a thin film is formed after forming abottom layer. Furthermore, the invention is not limited to magneticmaterials. The invention is applicable to various materials such as Si,and for carrying out reaction deposition with reaction gas such asoxygen and reaction deposition between multi-elements and gas. Theinvention can also provide properties which were obtained only by aconventional multi-layer process. For instance, the invention can beapplied to form an improved liquid crystal oriented film, transparentelectrode film and capacitor which could not have been obtained from aconventional vacuum deposition method.

Reaction gas mentioned in the invention generates a chemical reaction ina film which is formed by vacuum deposition, and is then absorbed by thefilm. If a high-frequency excitation is also carried out in theinvention, any gas except inert gas can be applicable. In addition tothe oxygen gas mentioned above, ozone gas or the like can also beapplied. Reaction with nitrogen monoxide, nitrogen dioxide, carbonmonoxide, carbon dioxide, chlorine gas or the like is also possible inthe invention. In an active atmosphere such as a high-frequencyexcitation atmosphere, nitrogen gas also functions as reaction gas as itdoes in a sputtering method. A preferable degree of vacuum during vacuumdeposition depends on an evaporation source. However, the degree whichis applied for a general vacuum deposition process is applicable to forma film in the invention. More specifically, the degree of deposition is1×10⁻² torr or less. Different from a resistance heating method or aninduction heating method, 1×10⁻³ torr or less degree of deposition ispreferably applied in an electron beam deposition method so as toprovide a high voltage beam stably. However, if differential pressurewith a film forming region is maintained by a differential pressureplate or the like, the degree of vacuum of the film forming region canbe more than 1×10⁻³. When an ion beam deposition is applied, the degreeof vacuum around an ion source should be considered.

The flux of gas should be kept orderly by setting a nozzle and a filmforming section as close as possible in a poor quality of vacuum (highpressure) atmosphere, so that the disorder of gas flux and collisionamong atoms are prevented. The frequency of collision decreasessignificantly with 1×10⁻⁴ torr or less degree of pressure. Thus, it ispreferable to form a thin film with 1×10 −⁴ torr degree of vacuum. Thereis no particular limitation on the number of nozzles. However, when morethan one nozzle is applied, the flux of gas becomes disorderly as soonas gas flows cross each other. Thus, the nozzles should be disposedwithout crossing gas flows.

Furthermore, the incidence angle of deposition is not limited to the onementioned in the examples. The incidence angle can be changed inaccordance with various purposes and objectives.

Besides an electron beam deposition method, other deposition methodssuch as an induction heating method, a resistance heating method and anion plating method can also be applied in the invention. In addition toa continuous deposition method of shifting from a high incidence angleto a low incidence angle mentioned in the example of the invention, acontinuous deposition method of shifting from a low incidence angle to ahigh incidence angle, or a continuous deposition method applying mainlya vertical incidence angle can also be applied in the invention. Anotherdeposition method in which a substrate is deposited with or withoutbeing rotated is also applicable to the invention, so that the amount ofintroduced gas can be reduced.

The invention may be embodied in other forms without departing from thespirit or essential characteristics thereof. The embodiments disclosedin this application are to be considered in all respects as illustrativeand not restrictive, the scope of the invention is indicated by theappended claims rather than by the foregoing description, and allchanges which come within the meaning and range of equivalency of theclaims are intended to be embraced therein.

What is claimed is:
 1. A device for manufacturing a thin film comprisinga supporting body for supporting a long macromolecular substrate, ashielding plate for regulating the direction of atoms forming a thinfilm, a nozzle for directing gas from a deposition end side of a mainaperture formed in said shielding plate to said substrate, and anothernozzle for orienting gas flux from a top side of a sub-aperture formedin said shielding plate on a deposition starting side of said mainaperture or from a section near said supporting body to selectivelydeposit a metal oxide on a surface of said substrate; said substraterunning in a vacuum along said supporting body; and said supporting bodybeing made of a seamless belt.
 2. A device for manufacturing a thin filmcomprising a supporting body for supporting a long macromolecularsubstrate, a shielding plate for regulating the direction of atomsforming a thin film, a nozzle for directing gas from a deposition endside of an aperture formed in said shielding plate, and a nozzle fordirecting gas flux from the outside of a circulating section of vaporforming said thin film to selectively deposit a metal oxide on a surfaceof said substrate; said substrate running in a vacuum along saidsupporting body; and said supporting body being made of a seamless belt.3. A device for manufacturing a thin film, comprising a supporting bodyfor supporting a long macromolecular substrate, a shielding plate forregulating the direction of atoms forming a thin film, and a nozzle fordirecting gas flux from a deposition end side of each of two aperturesfor depositing a deposition film in an intermittent manner, formed insaid shielding plate; said substrate running in a vacuum along saidsupporting body; and said supporting body being made of a seamless belt.